The prior art has shown certain compounds comprising substituted thiazolesulfenamides or thiazoles. One such reference discloses the compounds comprising the oxidative condensation products of organic mercaptans and amines. However, the amines which are used in the process of the prior art reference are stronger than ammonia, the amino nitrogen atoms possessing a dissociation constant greater than 1.8 .times. 10.sup..sup.-5. In contradistinction to this, the amines which are utilized as one of the starting materials to prepare the compounds of the present process are less basic than ammonia. In addition, another prior reference discloses sulfenamides which are prepared from primary amines and will possess only one substituent of the nitrogen other than hydrogen. The compound of this reference also differs from the compounds of the present invention which comprise disubstituted benzothiazole-2-sulfenamides in which one of the substituents is a phenyl radical. Other references which are found in the prior art include derivatives of N-betacyanoethylbenzothiazolesulfenamides in which each of the compounds disclosed in the reference requires the presence of a cyanoethyl substituent of the nitrogen atom. Another reference has been found in the prior art which discloses a diphenyl-substituted compound for use as a vulcanization accelerator. However, it is stated in the reference that the introduction of two phenyl radicals in the group of a sulfenamide compound results in a total loss of vulcanization activity while replacement of one phenyl radical with a hydrogen atom (in other words a mono-substituted sulfenamide) creates a compound which is an effective vulcanization accelerator. Other references have also disclosed substituted benzothiazolesulfenamides containing halogen atoms which are used as accelerators in the vulcanization of rubber or mono-substituted arylene thiazylsulfenamides which are also used as accelerators in the vulcanization of rubber. As will be hereinafter shown, this is in contradistinction to the findings of the present invention which discloses an effective vulcanization accelerator comprising a disubstituted sulfenamide, one of which is a phenyl radical and the other of which is an alkyl or cycloalkyl radical. Furthermore, there is no teaching in the art of the ability of the compounds of the present invention to decrease the scorch time in admixtures with an antiozonant and rubber.
This invention relates to novel compounds comprising N-phenyl-N-R-thiazole-2-sulfenamides in which the R is an alkyl or cycloalkyl radical of the type hereinafter set forth in greater detail.
The N,N-disubstituted-thiazole-2-sulfenamides which comprise the novel compounds of the present invention and in which one substituent on the nitrogen atom is a phenyl and the other substituent is an alkyl or cycloaklyl radical, will have varied utility. In particular, the compounds may be useful as additives to rubber. As a particular advantage in such use, the N,N-disubstituted-benzothiazole-2-sulfenamide serves to offset the decrease in scorch time which occurs when a secondary diamine antiozonant is incorporated in the rubber formulation. The phenyl and R groups in the above formula will be selected with reference to the particular rubber properties desired inasmuch as they appear to react somewhat differently in different rubber formulations.
In one aspect an embodiment of this invention resides in N-phenyl-N-R-benzothiazole-2-sulfenamide in which R is an alkyl radical of from 3 to about 20 carbon atoms or a cycloalkyl radical of from 4 to 6 carbon atoms.
A specific embodiment of this invention is found in a compound useful as a rubber additive comprising N-phenyl-N-butylbenzothiazole-2-sulfenamide.
Other objects and embodiments will be found in the following further detailed description of the present invention.
As hereinbefore set forth the present invention is concerned with novel compounds comprising N,N-disubstituted-benzothiazole-2-sulfenamides in which one of the substituents on the nitrogen atom is a phenyl radical while the other substituent is an alkyl radical containing from 3 to 20 carbon atoms and preferably in a range of from 3 to 12 carbon atoms, or a cycloalkyl radical containing from 4 to 12 carbon atoms and preferably from 4 to 6 carbon atoms. These compounds will possess the generic formula: N-phenyl-N-R-benzothiazole-2-sulfenamide, in which R possesses the above description. Illustrative novel compounds of the present invention will include N-phenyl-N-propylbenzothiazole-2-sulfenamide, N-phenyl-N-butylbenzothiazole-2-sulfenamide, N-phenyl-N-pentylbenzothiazole-2-sulfenamide, N-phenyl-N-hexylbenzothiazole-2-sulfenamide, N-phenyl-N-heptylbenzothiazole-2-sulfenamide, N-phenyl-N-octylbenzothiazole-2-sulfenamide, N-phenyl-N-nonylbenzothiazole-2-sulfenamide, N-phenyl-N-decylbenzothiazole-2-sulfenamide, N-phenyl-N-undecylbenzothiazole-2-sulfenamide, N-phenyl-N-dodecylbenzothiazole-2-sulfenamide, N-phenyl-N-tridecylbenzothiazole-2-sulfenamide, N-phenyl-N-tetradecylbenzothiazole-2-sulfenamide, N-phenyl-N-pentadecylbenzothiazole-2-sulfenamide, N-phenyl-N-hexadecylbenzothiazole-2-sulfenamide, N-phenyl-N-heptadecylbenzothiazole-2sulfenamide, N-phenyl-N-octadecylbenzothiazole-2-sulfenamide, N-phenyl-N-nonadecylbenzothiazole-2-sulfenamide, N-phenyl-N-eicosylbenzothiazole-2-sulfenamide, N-phenyl-N-cyclobutylbenzothiazole-2-sulfenamide, N-phenyl-N-cylclopentylbenzothiazole-2-sulfenamide, N-phenyl-N-cyclohexylbenzothiazole-2-sulfenamide, N-phenyl-N-cycloheptylbenzothiazole-2-sulfenamide, N-phenyl-N-cyclooctylbenzothiazole-2-sulfenamide, N-phenyl-N-cyclononylbenzothiazole-2-sulfenamide, N-phenyl-N-cyclodecylbenzothiazole-2-sulfenamide, N-phenyl-N-cycloundecylbenzothiazole-2-sulfenamide and N-phenyl-N-cyclododecylbenzothiazole-2-sulfenamide, etc. It is understood that the alkyl group may be of straight or branched chain and also of primary, secondary or tertiary configuration. -sulfenamide previously one or -sulfenamide
The N,N-disubstituted-thiazole-2-sulfenamide of the present invention may be prepared in any suitable manner. In a particularly preferred method, a thiazole-2sulfenamide is reacted with an arylamine acid salt such as an aniline acid salt. The thiazole-2-sulfenamide may be obtained from any suitable source or prepared in accordance with any of the various methods previous disclosed in the art. In a preferred embodiment, benzothiazole-2-sulfenamide is utilized as one of the reactants and, in another embodiment, the amide moiety may contain or two alkyl substituents, preferably containing from 3 to about 6 and more particularly from 3 to 4 carbon atoms. For example, N-tert-butylbenzothiazole-2sulfenamide is available in the open market and, as will be shown in the appended examples, has been used for the preparation of N-phenyl-N-R-substituted derivatives.
In this method of preparation, the thiazole-2-sulfenamide is reacted with an N-substituted aniline acid salt. Any suitable acid salt of aniline may be used. Particularly preferred salts will include the hydrohalide salts such as hydrochloride salts, hydrobromide salts, hydroiodide salts, etc., with the hydrochloride salts being especially preferred. Other acid salts include the sulfate, phosphate, nitrate, as well as organic acid salts and particularly the formate, acetate, propionate, butyrate, oxalate, malonate, benzoate salts, etc. When the R in the generic formula of the compound is alkyl, the acid salt of N-C.sub.3 -C.sub.20 -alkylaniline is used as a reactant and similarly when R in the formula is cycloalkyl, the acid salt of N-C.sub.4 -C.sub.12 -cycloalkylaniline is used as a reactant.
The aniline acid salt may be obtained from any suitable source or may be prepared in any suitable manner. A number of these acid salts are available commercially and accordingly are conveniently used in the present invention. The hydrochloride salt may be prepared, for example, by dissolving the aniline in a suitable solvent, such as diethyl ether, and adding concentration hydrochloric acid thereto, with intimate stirring until no further precipitation occurs. The precipitate is then filtered from the solution and washed with ether, followed by drying either in air or otherwise.
The thiazole-2-sulfenamide and the N-substituted aniline acid salt are reacted in any suitable manner. As a particular advantage to this method of preparation, the reaction occurs readily and, accordingly, required minimum time, which may range from 5 minutes to 1 hour and more particularly from 10 minutes to 30 minutes. The reaction is readily effected at room temperature although, when desired, a higher temperature may be used which preferably is below about 100.degree. C. The reaction is effected by forming a solution of one or both the reactants, which may be mildly heated to facilitate solubility. Any suitable solvent may be used and conveniently comprises an alcohol such as methanol, ethanol, propanol, butanol, etc., a ketone as acetone, methyl ethyl ketone, diethyl ketone, etc., dioxane, hydrocarbons such as benzene, toluene, pentane, hexane, etc., an amide such as dimethylformamide, etc., or mixtures of these with each other or with water. The solvent employed preferably is one in which both reactants are mutually soluble, although partial solubility of the reactants in the solvent may be satisfactory as with water, ether, etc., but may require longer time in mixing to insure complete reaction. Because the solvent is subsequently removed by evaporation, it is preferred to use a lower boiling solvent for ready evaporation from the product.
In instances where the thiazolesulfenamide for use as a reactant contains impurities, such as disulfides, it may be desirable to filter the solution of sulfenamide prior to commingling with the aniline acid salt. Similarly, when the aniline acid salt contains impurities which can be removed by filtering, the solution of the aniline acid salt preferably is filtered prior to use.
The thiazolesulfenamide and aniline acid salt are reacted in equimolar proportions. However, an excess of the sulfenamide or aniline acid salt may be employed, which excess generally will not exceed about 4:1 molar proportions and thus the reactants may be used in a mole proportion of from 1:1 to 4:1.
The thiazolesulfenamide and aniline acid salt are reacted in any suitable manner. As hereinbefore set forth, this requires merely intimate mixing of the reactants in contact with the solvent. In one method, the solid product may be removed by filtering and in another method, particularly when the product is soluble in the solvent, the solvent is evaporated in any suitable manner, preferably under vacuum, and the product recovered as a solid precipitate. The ammonium chloride or other ammonium salt formed in the reaction is removed in any suitable manner and preferably by washing with water. To facilitate removal of the ammonium salt, the solid may first be dissolved in ether and then water washed. The resultant mixture may be dried, in any suitable manner, such as by being contacted with magnesium sulfate, etc., and then the ether removed be evaporation. The product may be further purified as desired by crystallization from ether, benzene or other suitable agent.
While the above method of preparation is preferred, it is understood that any other suitable method may be used. One other method is reacting the thiazolesulfenamide with the N-substituted aniline at 30.degree. to about 100.degree. C. in a solvent and continuously removing the ammonia or amine evolved in the reaction. In still another method, the reaction is effected by the oxidative condensation in alcohol solvent and alkali metal hypochlorite at a temperature below 0.degree. C. Any other suitable method of preparation may be used.
As hereinbefore set forth, a preferred use is to offset the decrease in scorch time encountered when using an antiozonant. In one embodiment, the antiozonant is of the phenylenediamine type and includes, for example, N,N'-di-sec-alkyl-p-phenylenediamine in which the alkyl contains from 3 to 12 carbon atoms, N-phenyl-N'-sec-alkyl-p-phenylenediamine, in which the alkyl contains 3 to 12 carbon atoms, N,N'-dicyclohexyl-p-phenylenediamine, N-phenyl-N'-cyclohexyl-p-phenylenechlorine, etc. In another embodiment, the antiozonant is of the aminophenol type and includes N-C.sub.3 C.sub.20 -alkyl-p-aminophenol, N-cycloalkyl-p-aminophenol in which the cycloalkyl ring contains from 4 to 12 carbon atoms, etc. The antiozonant may be used in a concentration of from 1 to about 5 parts by weight per 100 parts of rubber hydrocarbon in the formulation.
The N,N-disubstituted-benzothiazole-2-sulfenamide of the present invention is used in the rubber formulation in a concentration of from 0.5 to about 3 and preferably from 1 to 2 parts of the sulfenamide per 100 parts of the rubber hydrocarbon in the formulation. The sulfenamide of the present invention is incorporated in the rubber formulation in any suitable manner and conveniently is incorporated during milling of the various ingredients including, in addition to the sulfenamide of the present invention, carbon, zinc oxide, sulfur, stearic acid, antioxidant, antiozonant, etc., all of these being used in conventional concentrations. As another means of controlling the curing of the rubber stock, additional compounds may also be included in rubber formulation as, for example, thiuram disulfides, N-alkyl-sulfenamides, cyclohexylamine, N-cyclohexylthiophthalimide, mercaptobenzothiazole or other sulfenamides, etc., and/or an excess of sulfur may be used. These additional compounds will be selected for use in conjunction with the N,N-disubstituted-benzothiazole-2-sulfenamide of the present invention to produce a formulation having the desired scorch time and the desired vulcanization to prepare a rubber product of desired physical properties. The vulcanization is effected in conventional manner.